EP0269583A2 - Méthode de préparation de résines de polyesters de haut poids moléculaire - Google Patents

Méthode de préparation de résines de polyesters de haut poids moléculaire Download PDF

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Publication number
EP0269583A2
EP0269583A2 EP87830402A EP87830402A EP0269583A2 EP 0269583 A2 EP0269583 A2 EP 0269583A2 EP 87830402 A EP87830402 A EP 87830402A EP 87830402 A EP87830402 A EP 87830402A EP 0269583 A2 EP0269583 A2 EP 0269583A2
Authority
EP
European Patent Office
Prior art keywords
granules
carbon dioxide
polycondensation
treatment
molecular weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87830402A
Other languages
German (de)
English (en)
Other versions
EP0269583B1 (fr
EP0269583A3 (en
Inventor
Hussain Ali-Kashif Al Ghatta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cobarr SpA
Original Assignee
Cobarr SpA
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Filing date
Publication date
Application filed by Cobarr SpA filed Critical Cobarr SpA
Priority to AT87830402T priority Critical patent/ATE90953T1/de
Publication of EP0269583A2 publication Critical patent/EP0269583A2/fr
Publication of EP0269583A3 publication Critical patent/EP0269583A3/en
Application granted granted Critical
Publication of EP0269583B1 publication Critical patent/EP0269583B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers

Definitions

  • This invention relates to a method for producing high molecular weight polyester resin, wherein granules of resin, in particular of polyethyleneterephtalate, are subjected to solid state polycondensation.
  • High molecular weight polyester resins have been produced in the solid state at a lower temperature than the polymer melting temperature and either under a vacuum or an inert gas atmosphere.
  • Such prior methods require, preparatory to polycondensation, partial or total crystallization of the granules under agitation, for example in either rotary units under vacuum or fluidized bed units, in order to prevent the granules from becoming stuck during polymerization. In fact, such sticking may turn the granules into a single lump, bringing the plant to a standstill.
  • the granules of amorphous polymer in the methods disclosed in the above-mentioned patents need to be forcibly stirred at a first crystallization stage before the granules can be passed to a solid state polycondensation stage on a fixed bed.
  • polyester granules must be stirred at a stage preceding the polycondensation stage is the cause for releasing large amounts of polymer dust and a high power consumption.
  • the polymer dust as produced by fretting of the mechanical stirring devices against the granules and between granules, may create serious problems at the succeeding polycondensation stage, and the mechanical stirring devices are often a cause for stopping the plant either for servicing purposes or on account of malfunction of the stirrers, which are subjected to high mechanical stresses.
  • the method comprises the step of treating the granules, prior to polycondensation, with carbon dioxide at a higher temperature than the critical temperature of carbon dioxide.
  • the treatment is carried out with carbon dioxide in a supercritical condition.
  • the amorphous polyester granules are effectively prevented from sticking to one another during the solid state polycondensation on a fixed bed.
  • the granules of amorphous polyester are preferably subjected to an atmosphere containing carbon dioxide at a pressure in excess of 25 bars and at a lower temperature than the polymer melting temperature (approximately 240°C) for a sufficient time period to enable access to the polycondensation step without any risk of the granules becoming stuck together.
  • This treatment time is normally in the range of 0.5 to 5 hours.
  • a further advantage of the method according to the invention is that the amount of acetaldehyde present in the granules and the rate of acetaldehyde formation in the granules can be lowered. This significant side effects seemingly arise from that the carbon dioxide extracts the acetaldehyde from the granules and deactivates the catalysts in the granules themselves.
  • the solid state polycondensation is carried out at a temperature within the range of 180°C to 240°C, preferably of 200°C to 230°C.
  • Carbon dioxide, or another inert gas such as nitrogen, can be advantageously used at the polycondensation stage in a ratio of 0.4-3 kg/hour inert gas per kg/hour granules.
  • the residence time of granules in the polycondensation stage was 20 hours.
  • the CO2 coming out from the polycondensation stage was cycled back following purification of the volatile substances formed during the polycondensation.
  • the PET granules yielded by the polycondensation stage had an acetaldehyde content of 0.4 ppm and an acetaldehyde generation rate at 270°C of 0.25 ppm acetaldehyde/minute.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Looms (AREA)
  • Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
  • Radar Systems Or Details Thereof (AREA)
EP87830402A 1986-11-21 1987-11-12 Méthode de préparation de résines de polyesters de haut poids moléculaire Expired - Lifetime EP0269583B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87830402T ATE90953T1 (de) 1986-11-21 1987-11-12 Verfahren zur herstellung von hochmolekularen polyesterharzen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT22424/86A IT1199668B (it) 1986-11-21 1986-11-21 Procedimento per la produzione di resina poliestere ad alto peso molecolare
IT2242486 1986-11-21

Publications (3)

Publication Number Publication Date
EP0269583A2 true EP0269583A2 (fr) 1988-06-01
EP0269583A3 EP0269583A3 (en) 1990-01-31
EP0269583B1 EP0269583B1 (fr) 1993-06-23

Family

ID=11196125

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87830402A Expired - Lifetime EP0269583B1 (fr) 1986-11-21 1987-11-12 Méthode de préparation de résines de polyesters de haut poids moléculaire

Country Status (7)

Country Link
EP (1) EP0269583B1 (fr)
AT (2) ATE90953T1 (fr)
DE (1) DE3786329T2 (fr)
IL (1) IL84455A (fr)
IN (1) IN169466B (fr)
IT (1) IT1199668B (fr)
TR (1) TR23950A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0300981A1 (fr) * 1987-07-24 1989-01-25 COBARR S.p.A. Un procédé pour la réduction des impuretés dans les résines polyesters
EP0334314A2 (fr) * 1988-03-23 1989-09-27 Mitsubishi Gas Chemical Company, Inc. Méthode de préparation de résins polycarbonate purifiée
EP0376119A2 (fr) * 1988-12-27 1990-07-04 COBARR S.p.A. Procédé pour recycler des bouteilles de boisson en PET
EP0419400A2 (fr) * 1989-09-18 1991-03-27 Shell Internationale Researchmaatschappij B.V. Procédé pour la cristallisation de polynaphtalate d'éthylène
WO1994001484A1 (fr) * 1992-07-06 1994-01-20 Buehler Ag Procede de reduction de l'indice de jaune d'un granulat polyester postcondense
US5656719A (en) * 1995-02-20 1997-08-12 Ems-Inventa Ag Condensation injection molding process for producing bottle preforms of polyethylene terephthalate and/or its copolyesters and resultant preforms

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA964546B (en) * 1995-06-06 1996-12-12 Univ North Carolina Process for the preparation of polyester in carbon dioxide
US6288202B1 (en) 1997-04-11 2001-09-11 The University Of North Carolina At Chapel Hill Synthesis of polycarbonates using Co2

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161578A (en) * 1978-05-12 1979-07-17 Bepex Corporation Process for solid phase polymerization of polyester
DE3323940A1 (de) * 1983-07-02 1985-01-10 Hoechst Ag, 6230 Frankfurt Verfahren zur reinigung von polymeren
EP0227608A1 (fr) * 1985-11-19 1987-07-01 COBARR S.p.A. Procédé de traitement d'articles creux, en particulier de préformes en téréphtalate de polyéthylène
EP0300981A1 (fr) * 1987-07-24 1989-01-25 COBARR S.p.A. Un procédé pour la réduction des impuretés dans les résines polyesters

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3544525A (en) * 1968-03-26 1970-12-01 Allied Chem Process for crystallization,drying and solid-state polymerization of polyesters

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161578A (en) * 1978-05-12 1979-07-17 Bepex Corporation Process for solid phase polymerization of polyester
DE3323940A1 (de) * 1983-07-02 1985-01-10 Hoechst Ag, 6230 Frankfurt Verfahren zur reinigung von polymeren
EP0227608A1 (fr) * 1985-11-19 1987-07-01 COBARR S.p.A. Procédé de traitement d'articles creux, en particulier de préformes en téréphtalate de polyéthylène
EP0300981A1 (fr) * 1987-07-24 1989-01-25 COBARR S.p.A. Un procédé pour la réduction des impuretés dans les résines polyesters

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0300981A1 (fr) * 1987-07-24 1989-01-25 COBARR S.p.A. Un procédé pour la réduction des impuretés dans les résines polyesters
EP0334314A2 (fr) * 1988-03-23 1989-09-27 Mitsubishi Gas Chemical Company, Inc. Méthode de préparation de résins polycarbonate purifiée
EP0334314A3 (en) * 1988-03-23 1990-07-25 Mitsubishi Gas Chemical Company, Inc. Method for producing purified polycarbonate resins
EP0376119A2 (fr) * 1988-12-27 1990-07-04 COBARR S.p.A. Procédé pour recycler des bouteilles de boisson en PET
EP0376119A3 (fr) * 1988-12-27 1991-01-09 COBARR S.p.A. Procédé pour recycler des bouteilles de boisson en PET
EP0419400A2 (fr) * 1989-09-18 1991-03-27 Shell Internationale Researchmaatschappij B.V. Procédé pour la cristallisation de polynaphtalate d'éthylène
EP0419400A3 (en) * 1989-09-18 1992-04-22 The Goodyear Tire & Rubber Company Process for crystallization of polyethylene naphthalate
WO1994001484A1 (fr) * 1992-07-06 1994-01-20 Buehler Ag Procede de reduction de l'indice de jaune d'un granulat polyester postcondense
US5656719A (en) * 1995-02-20 1997-08-12 Ems-Inventa Ag Condensation injection molding process for producing bottle preforms of polyethylene terephthalate and/or its copolyesters and resultant preforms

Also Published As

Publication number Publication date
IN169466B (fr) 1991-10-19
AT398574B (de) 1994-12-27
EP0269583B1 (fr) 1993-06-23
EP0269583A3 (en) 1990-01-31
ATA305287A (de) 1994-05-15
IL84455A0 (en) 1988-04-29
DE3786329D1 (de) 1993-07-29
IT8622424A1 (it) 1988-05-21
IT8622424A0 (it) 1986-11-21
DE3786329T2 (de) 1993-10-28
ATE90953T1 (de) 1993-07-15
TR23950A (tr) 1990-12-21
IT1199668B (it) 1988-12-30
IL84455A (en) 1991-07-18

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